3-Arylbenzofuranones as stabilizers

ABSTRACT

The invention described novel compounds of formulawherein the general symbols are as defined in claim 1, as stabilizers for protecting organic materials, in particular polymers and lubricants, against thermal, oxidative or light-induced degradation.

This application is a continuation of Ser. No. 09/121,583 filed on Jul.23, 1998 which is a divisional of application Ser. No. 08/867,111, filedon Jun. 2, 1997, now U.S. Pat. No. 5,814,692, issued on Sep. 29, 1998,which is a divisional of application Ser. No. 08/606,896, filed on Feb.26, 1996, now U.S. Pat. No. 5,773,631, issued on Jun. 30, 1998, which isa divisional of application Ser. No. 08/304,468, filed on Sep. 12, 1994,now U.S. Pat. No. 5,516,920, issued on May 14, 1996.

The present invention relates to novel 3-arylbenzofuranones, tocompositions comprising an organic material, preferably a polymer or alubricant, and to the novel stabilisers, as well as to the use thereoffor stabilising organic materials against oxidative, thermal orlight-induced degradation.

Individual 3-arylbenzofuran-2-ones are known in the literature and havebeen described, inter alia, by J. Morvan et al., Bull. Soc. Chim. Fr.1979, 583.

The use of some 3-phenyl-3H-benzofuran-2ones as stabilisers for organicpolymers is disclosed, inter alia in U.S. Pat. No. 4,325,863; U.S. Pat.No. 4,338,244 and U.S. Pat. No. 5,175,312.

It has now been found that a selected group of 3-arylbenzofuran-2-onesis particularly suitable for use as stabilisers for organic materialsthat are susceptible to oxidative, thermal or light-induced degradation.

Accordingly, the invention relates to compounds of formula I

wherein, when n is 1,

R₁ is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl,5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl,naphtho[2,3-b]thieyl, thiathrenyl, dibenzofuryl, chromenyl, xanthenyl,phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl,quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl,β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl,phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl,biphenyl, terphenyl, fluorenyl or phenoxazinyl, each unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy,halogen, amino, C₁-C₄alkylamino, phenylamino or di(C₁-C₄alkyl)amino, orR₁ is a radical of formula II

and

when n is 2

R₁ is phenylene or naphthylene which is unsubstituted or substituted byC₁-C₄alkyl or hydroxy; or is —R₁₂—X—R₁₃—,

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,chloro, hydroxy, C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; C₁-C₁₈alkoxy, C₁-C₈alkylthio, C₁-C₄alkylamino,di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino,C₃-C₂₅alkenoyloxy, C₃-C₂₅alkanoyloxy which is interrupted by oxygen,sulfur or N—R₁₄; C₆-C₈cycloalkylcarbonyloxy, benzoyloxy orC₁-C₁₂alkyl-substituted benzoyloxy; with the proviso that, when R₂ ishydrogen or methyl, R₇ or R₉ is not hydroxy or C₁-C₂₅alkanoyloxy, oreach pair of substituents R₂ and R₃ or R₃ and R₄ or R₄ and R₅, togetherwith the linking carbon atoms, forms a benzene ring; R₄ is additionally—(CH₂)_(p)—COR₁₅ or —(CH₂)_(q)OH, or when R₃, R₅ and R₆ are hydrogen, R₄is additionally a radical of formula III

wherein R₁ is as defined above for n=1,

R₆ is hydrogen or a radical of formula IV

in which R₄ is not a radical of formula III and R₁ is as defined abovefor n=1, R₇, R₈, R₉ and R₁₀ are each independently of one anotherhydrogen, halogen, hydroxy, C₁-C₂₅alkyl, C₂-C₂₅alkyl which isinterrupted by oxygen, sulfur or N—R₁₄; C₁-C₂₅-alkoxy, C₂-C₂₅alkoxywhich is interrupted by oxygen, sulfur or N—R₁₄; C₁-C₂₅alkylthio,C₃-C₂₅alkenyl, C₃-C₂₅alkenyloxy, C₃-C₂₅alkynyl, C₃-C₂₅alkynyloxy,C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedphenoxy; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;C₁-C₄alkylamino, di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyl, C₃-C₂₅alkanoylwhich is interrupted by oxygen, sulfur or N—R₁₄; C₁-C₂₅alkanoyloxy,C₃-C₂₅alkanoyloxy which is interrupted by oxygen, sulfur or N—R₁₄;C₁-C₂₅alkanoylamino, C₃-C₂₅alkenoyl, C₃-C₂₅alkenoyl which is interruptedby oxygen, sulfur or N—R₁₄; C₃-C₂₅alkenoyloxy which is interrupted byoxygen, sulfur or N—R₁₄; C₆-C₉cycloalkylcarbonyl,C₆-C₉cycloalkylcarbonyloxy, benzoyl or C₁-C₁₂alkyl-substituted benzoyl;benzoyloxy or C₁-C₁₂alkyl-substituted benzoyloxy;

or also in formula II each pair of substitutents R₇ and R₈ or R₈ andR₁₁, together with the linking carbon atoms, forms a benzene ring,

R₁₁ is hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkylthio, C₃-C₂₅alkenyl,C₃-C₂₅alkynyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;C₁-C₄alkylamino, di(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyl, C₃-C₂₅alkanoylwhich is interrupted by oxygen, sulfur or N—R₁₄; C₁-C₂₅alkanoylamino,C₃-C₂₅alkenoyl, C₃-C₂₅alkenoyl which is interrupted by oxygen, sulfur orN—R₁₄; C₆-C₉cycloalkylcarbonyl, benzoyl or C₁-C₁₂alkyl-substitutedbenzoyl; with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ isnot hydrogen, R₁₂ and R₁₃ are each independently of the otherunsubstituted or C₁-C₄alkyl-substituted phenylene or naphthylene,

R₁₄ is hydrogen or C₁-C₈alkyl,

R₁₅ is hydroxy,

R₁₆ and R₁₇ are each independently of the other hydrogen CF₃,C₁-C₁₂alkyl or phenyl, or

R₁₆ and R₁₇, together with the linking carbon atom, form aC₅-C₈cycloalkylidene ring which is unsubstituted or substituted by 1 to3 C₁-C₄alkyl groups;

R₁₈ and R₁₉ are each independently of the other hydrogen, C₁-C₄alkyl orphenyl,

R₂₀ is hydrogen or C₁-C₄alkyl,

R₂₁ is hydrogen, unsubstituted or C₁C₄alkyl-substituted phenyl;C₁-C₂₅alkyl, C₂-C₂₅alkyl which is interrupted by oxygen, sulfur orN—R₁₄; C₇-C₉phenylalkyl which is unsubstituted or substituted in thephenyl moiety by 1 to 3 C₁-C₄alkyl groups; C₇-C₂₅phenylalkyl which isinterrupted by oxygen, sulfur or N—R₁₄ and which is unsubstituted orsubstituted in the phenyl moiety by 1 to 3 C₁-C₄alkyl groups; or R₂₀ andR₂₁, together with the linking carbon atoms, form aC₅-C₁₂cycloalkylidene ring which is unsubstituted or substituted by 1 to3 C₁-C₄alkyl groups;

R₂₂ is hydrogen or C₁-C₄alkyl,

R₂₃ is hydrogen, C₁-C₂₅alkanoyl, C₃-C₂₅alkenoyl, C₃-C₂₅alkanoyl which isinterrupted by oxygen, sulfur or N—R₁₄; C₂-C₂₅alkanoyl which issubstituted by a di(C₁-C₆alkyl)phosphonate group;C₆-C₉cycloalkylcarbonyl, thenoyl, furoyl, benzoyl orC₁-C₁₂alkyl-substituted benzoyl;

R₂₄ and R₂₅ are each independently of the other hydrogen or C₁-C₁₈alkyl,

R₂₆ is hydrogen or C₁-C₈alkyl,

R₂₇ is a direct bond, C₁C₁₈alkylene, C₂-C₁₈alkylene which is interruptedby oxygen, sulfur or N—R₁₄; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene,unsubstituted or C₁-C₄alkyl-substituted phenylene,

R₂₈ is hydroxy,

R₂₉ is oxygen —NH— or

R₃₀ is C₁-C₈alkyl or phenyl,

R₃₁ is hydrogen or C₁-C₁₈alkyl,

M is a metal cation of valency r,

X is a direct bond, oxygen, sulfur or —NR₃₁—,

N is 1 or 2

p 0, 1 or 2,

q is 1,2,3,4,5 or 6

r is 1,2 or 3, and

s is 0, 1 or 2

Naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl,5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thiathrenyl, dibenzofuryl, chromenyl, xanthenyl,phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl,quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl,β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl,phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl,biphenyl, terphenyl, fluorenyl or phenoxazinyl, each unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy,halogen, amino, C₁-C₄alkylamino, phenylamino or di(C₁-C₄alkyl)amino,will typically be 1-naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl,1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl,2methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl,1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl,1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6naphthyl,1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl,1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl,1,4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl,9-anthryl, 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]-thienyl,4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl,8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiinyl, 2,7-phenoxathiinyl,2-pyrrolyl, 3-pyrrolyle, 5-methyl-3-pyrrolyl, 2-imidazolyl,4-imidazolyl, 5-imidazolyl, 2-methyl, 4-imidazolyl, 2ethyl-4-imidazolyl,2-ethyl-5-imidazolyl, 3-pyrazolyl, 1-methyl-3-pyrazolyl,1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl,2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl,1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl,1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl,2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl,6-isoquinolyl, 7-isoquinolyl, isoquinolyl, 3-methoxy-6-isoquinolyl,2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl,2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl,1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl,1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl,2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl,2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl,3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl,2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl,2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl,9-methyl-3-carbazolyl, β-carbolin-3-yl, 1methyl-β-carbolin-3-yl,1-methyl-β-carbolin, 6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl,2-perimidinyl, 1-methyl-5-perimidinyl, 5-phenanthrolinyl,6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl,10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl,4-methyl-3-furazanyl, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl.

Particularly preferred above substitutents are naphthyl, phenanthryl,anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl,thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thiathrenyl,dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl,isoindolyl, indolyl, phenothiazinyl, biphenyl, terphenyl, fluorenyl orphenoxazinyl each unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy, phenylamino ordi(C₁-C₄alkyl)amino, typically 1-naphthyl, 2-naphthyl,1-phenylamino-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl,1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl,1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl,1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl,1,4-dihydroxy-2naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl,3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuryl,4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl,8-methyl-2-xanthenyl, 3-xanthenyl, 2-pyrrolyl, 3-pyrrolyl,2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl.

Halogen substitutents will conveniently be chloro, bromo or iodo. Chlorois preferred.

Alkanoyl of up to 25 carbon atoms inclusive is a branched or unbranchedradical, typically including formyl, acetyl, propionyl, butanoyl,pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl,undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl,hexadecanoyl, heptadecanoyl, octadecanoyl, eicosanoyl or docosanoyl.Alkanoyl of 2 to 18, most preferably 2 to 12, e.g. 2 to 6, carbon atoms,is preferred. Acetyl is particularly preferred.

C₂-C₂₅Alkanoyl substituted by a di(C₁-C₆alkyl) phosphonate group willtypically be (CH₃CH₂O)₂ POCH₂CO—, (CH₃O)₂POCH₂CO—, (CH₃CH₂ CH₂CH₂O)₂POCH₂CO—, (CH₃CH₂O)₂ POCH₂CH₂CO—, (CH₃O)₂ POCH₂CH₂CO—,(CH₃CH₂CH₂CH₂O)₂POCH₂CH₂CO—, (CH₃CH₂O)₂PO (CH₂)₄CO—,(CH₃CH₂O)₂PO(CH₂)₈CO— or (CH₃CH₂O)₂ PO(CH₂)₁₇CO—.

Alkanoyloxy of up to 25 carbon atoms is an unbranched or branchedradical and is typically formyloxy, acetoxy, propionyloxy, butanoyloxy,pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy,decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy,tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy,octadecanoyloxy, eicosanoyloxy or docosanoyloxy. Alkanoyloxy of 2 to 18,preferably 2 to 12, e.g. 2 to 6, carbon atoms is preferred. Acetoxy isparticularly preferred.

Alkenoyl of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl,n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-2-octenoyl, n-2-dodecenoyl,isododecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl. Alkenoyl of3 to 18, preferably 3 to 12, e.g. 3 to 6, most preferably 3 to 4, carbonatoms is preferred.

C₃-C₂₅Alkenoyl interrupted by oxygen, sulfur or N—R₁₄ is typicallyCH₃OCH₂CH₂CH═CHCO— or CH₃OCH₂CH₂OCH═CHCO—.

Alkenoyloxy of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propenoyloxy, 2-butenoyloxy, 3-butenoyloxy,isobutenoyloxy, n-2,4-pentadienoyloxy, 3-methyl-2-butenoyloxy,n-2-octenoyloxy, n-2-dodecenoyloxy, isododecenoyloxy, oleoyloxy,n-2-octadecenoyloxy or n-4-otadecenoyloxy. Alkenoyloxy of 3 to 18,preferably 3 to 2, typically 3 to 6, most preferably 3 to 4, carbonatoms is preferred.

C₃-C₂₅Alkenoyloxy interrupted by oxygen, sulfur or N—R₁₄ will typicallybe CH₃OCH₂CH₂CH═CHCOO— or CH₃OCH₂CH₂OCH═CHCOO—.

C₃-C₂₅-Alkanoyl interrupted by oxygen, sulfur or N—R₁₄ will typically beCH₃—O—CH₂CO—, CH₃—S—CH₂CO—, CH₃—NH—CH₂CO—, CH₃—N(CH₃)—CH₂CO—,CH₃—O—CH₂CH₂—O—CH₂CO—, CH₃—(O—CH₂CH₂—)₂O—CH₂CO—,CH₃—(O—CH₂CH₂—)₃O—CH₂CO— or CH₃—(O—CH₂CH₂—)₄O—CH₂CO—.

C₃-C₂₅-Alkanoyloxy interrupted by oxygen, sulfur or N—R₁₄ will typicallybe CH₃—O—CH₂COO—, CH₃—S—CH₂COO—, CH₃—NH—CH₂COO—, CH₃—N(CH₃)—CH₂COO—,CH₃O—CH₂CH₂—O—CH₂COO—, CH₃—(O—CH₂CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂COO— orCH₃—(O—CH₂CH₂—)₄O—CH₂COO—.

C₆-C₉Cycloalkylcarbonyl is typically cyclopentylcarbonyl,cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl.Cyclohexylcarbonyl is preferred.

C₆-C₉Cycloalkylcarbonyloxy is typically cyclopentylcarbonyloxy,cyclohexylcarbonyloxy, cycloheptycarbonyloxy or cyclooctylcarbonyloxy.Cyclohexylcarbonyloxy is preferred.

C₁-C₁₂Alkyl-substituted benzoyl which preferably carries 1 to 3, mostpreferably 1 or 2, alkyl groups, is typically o-, m- or p-methylbenzoyl,2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl, 2,5-dimethylbenzoyl,2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethylbenzoyl,2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl 2-ethylbenzoyl,2,4,6-trimethylbenzoyl, 2,6-dimethyl-4-tert-butylbenzoyl or3,5-di-tert-butylbenzoyl. Preferred substituents are C₁-C₈alkyl, mostpreferably C₁-C₄alkyl.

C₁-C₁₂Alkyl-substituted benzoyloxy which preferably carries 1 to 3, mostpreferably 1 or 2, alkyl groups, is typically o-,m- orp-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethylbenzoyloxy,2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy,3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy,4-tert-butylbenzoyloxy, 2-ethylbenzoyloxy, 2,4,6-trimethylbenzoyloxy,2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy.Preferred substituents are C₁-C₈alkyl, preferably C₁-C₄alkyl.

Alkyl of up to 25 carbon atoms is a branched or unbranched radical andis typically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetrmethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl heptadecyl, octadecyleicosyl or docosyl. A preferred meaning of R₂ and R₄ is typicallyC₁-C₁₈alkyl. A particularly preferred meaning of R₄ is C₁-C₄alkyl.

Alkenyl of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propenyl 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Alkenyl of 3 to18, preferably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbonatoms is preferred.

Alkenyloxy of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propenyloxy, 2-butenyloxy, 3-butenyloxy,isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2-butenyloxy,n-2-octenyloxy, n-2-dodecenyloxy, isododecenyloxy, oleyloxy,n-2-octadecenyloxy or n-4-octadecenyloxy. Alkenyloxy of 3 to 18,preferably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbonatoms is preferred.

Alkynyl of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propynyl (—CH₂—C≡CH), 2-butynyl, 3-butynyl,n-2-octynyl or n-2-dodecynyl. Alkynyl of 3 to 18, preferably 3 to 12,typically 3 to 6, most preferably 3 to 4, carbon atoms is preferred.

Alkynyloxy of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propynyloxy (—OCH₂—C≡CH), 2-butynyloxy,3-butynyloxy, n-2-octynyloxy, or n-2-dodecynyloxy. Alkynyloxy of 3 to18, preferably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbonatoms is preferred.

C₂-C₂₅Alkyl interrupted by oxygen, sulfur or >N—R₁₄ will typically beCH₃—O—CH₂—, CH₃—S—CH₂—, CH₃—NH—CH₂—, CH₃—N(CH₃)—CH₂—,CH₃—O—CH₂CH₂—O—CH₂—, CH₃—(O—CH₂CH₂—)₂O—CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂— orCH₃—(O—CH₂CH₂—)₄O—CH₂—.

C₇-C₉Phenylalkyl may typically be benzyl, α-methylbenzyl,α,α-dimethylbenzoyl or 2-phenylethyl. Benzyl and α,α-dimethylbenzyl arepreferred.

C₇-C₉Phenylalkyl which is unsubstituted or substituted in the phenylmoiety by 1 to 3 C₁-C₄alkyl groups will typically be benzyl,α-methylbenzyl, α,α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl,3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzylor 4-tert-butylbenzyl. Benzyl is preferred.

C₇-C₂₅Phenylalkyl which is interrupted by oxygen, sulfur or >N—R₁₄ andis unsubstituted or substituted in the phenyl moiety by 1 to 3C₁-C₄alkyl groups is a branched or unbranched radical such asphenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl,4-methylphenoxymethyl, 2,4-dimethylphenoxymethyl,2,3-dimethyphenoxymethyl, phenylthiomethyl, N-methyl-N-phenyl-methyl,N-ethyl-N-phenylmethyl, 4-tert-butylphenoxymethyl,4-tert-butylphenoxyethoxymethyl, 2,4-di-tert-butylphenoxymethyl,2,4-di-tert-butylphenoxyethoxymethyl, phenoxyethoxyethoxyethoxymethyl,benzyloxymethyl, benzyloxyethoxymethyl, N-benzyl-N-ethylmethyl orN-benzyl-N-isopropyl-methyl.

C₇-C₉Phenylalkoxy is typically benzyloxy, α-methylbenzyloxy,α,α-dimethylbenzyloxy or 2-phenylethoxy. Benzyloxy is preferred.

C₁-C₄Alkyl-substituted phenyl that preferably contains 1 to 3,preferably 1 or 2, alkyl groups, will typically be o-, m- orp-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

C₁-C₄Alkyl-substituted phenoxy which preferably contains 1 to 3, mostpreferably 1 or 2, alkyl groups, is typically o-, m- or p-methylphenoxy,2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy,2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or2,6di-ethylphenoxy.

Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl is typicallycyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl,methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,tert-butylcyclohexyl, cyclopheptyl or cyclooctyl. Cyclohexyl andtert-butylcyclobexyl are preferred.

Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy is typicallycyclopentoxy, methylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy,methylcyclohexoxy, dimethylcyclohexoxy, trimethylcyclohexoxy,tert-butylcyclohexoxy, cycloheptoxy or cyclooctoxy. Cyclohexoxy andtert-butylcyclohexoxy are preferred.

Alkoxy of up to 25 carbon atoms is a branched or unbranched radical andis typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy,hexadecyloxy or octadecyloxy. Alkoxy of 1 to 12, preferably 1 to 8, e.g.1 to 6, carbon atoms is preferred.

C₂-C₂₅Alkoxy interrupted by oxygen, sulfur or >NR₁₄ is typicallyCH₃—O—CH₂CH₂O—, CH₃—S—CH₂CH₂O—, CH₃—NH—CH₂CH₂O—, CH₃N(CH₃)—CH₂CH₂O—,CH₃—O—CH₂CH₂—O—CH₂CH₂O—, CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂O—,CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂O— or CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂O—.

Alkylthio of up to 25 carbon atoms is a branched or unbranched radicaland is typically methylthio, ethylthio, propylthio, isopropylthio,n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio,heptylthio, octylthio, decylthio, tetradecylithio, hexadecylthio oroctadecylthio. Alkylthio of 1 to 12, preferably 1 to 8, e.g. 1 to 6,carbon atoms is preferred.

Alkylamino of up to 4 carbon atoms is a branched or unbranched radicaland is typically methylamino, ethylamino, propylamino, isopropylamino,n-butylamino, isobutylamino or tert-butylamino.

Di(C₁-C₄)alkylamino also signifies that the two moieties, eachindependently of the other, are branched or unbranched, and is typicallydimethylamino, methylethylamino, diethylamino, methyl-n-propylamino,methylisopropylamino, methyl-n-butylamino, methylisobutylamino,ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino,ethyl-tert-butylamino, diethylamino, diisopropylamino,isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino ordiisobutylamino.

Alkanoylamino of up to 25 carbon atoms is an unbranched or branchedradical and is typically formylamino, acetylamino, propionylamino,butanoylamino, pentanoylamino, hexanoylamino, heptanoylamino,octanoylamino, nonanoylamino, decanoylamino, undecanoylamino,dodecanoylamino, tridecanoylamino, tetradecanoylamino,pentadecanoylamino, hexadecanoylamino, heptadecanoylamino,octadecanoylamino, eicosanoylamino oder docosanoylamino. Alkanoylaminoof 2 to 18, preferably 2 to 12, e.g. 2 to 6, carbon atoms is preferred.

C₁-C₁₈Alkylene is a branched or unbranched radical, typically methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,hexamethylene, hexamethylene, octanethylene, decamethylene,dodecamethylene or octadecamethylene. C₁-C₁₂Alkylene is preferred, andC₁-C₈alkylene is particularly preferred.

A C₁-C₄alkyl-substituted C₅-C₁₂cycloalkylene ring which preferablycontains 1 to 3, preferably 1 to 2 branched or unbranched alkyl groupswill typically be cyclopentylene, methylcyclopentylene,dimethylcyclopentylene, cyclohexylene, methylcyclohexylene,dimethylcyclohexylerie, trimethylcyclohexylene, tert-butylcyclohexylene,cycloheptylene, cyclooctylene or cyclodecylene. Cycloheylene andtert-butylcyclohexylene.

C₂-C₁₈Alkylene which is interrupted by oxygen, sulfur or >N—R₁₄ willtypically be —CH₂—O—CH₂—, —CH₂—S—CH₂—, —CH₂—NH—CH₂—, —CH₂—N(CH₃)—CH₂—,—CH₂—O—CH₂CH₂—O—CH₂—, —CH₂—(O—CH₂CH₂—)₂O—CH₂—, —CH₂—(O—CH₂CH₂—)₃O—CH₂—,—CH₂—(O—CH₂CH₂—)₄O—CH₂— or —CH₂CH₂—S—CH₂CH₂—.

C₂-C₁₈Alkenylene is typically vinylene, methylvinylene, octenylethyleneor dodecenylelhylene, C₂-C₈Alkenylene is preferred.

Alkylidene of 2 to 20 carbon atoms may typically be ethylidene,propyliden, butylidene, pentylidene, 4-methylpentylidene, heptylidene,nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene,1-ethylpropylidene or 1-ethylpentylidene, C₂-C₈Alkylidene is preferred.

Phenylalkylidene of 7 to 20 carbon atoms may typically be benzylidene,2-phenylethylidene or 1-phenyl-2-hexylidene. C₇-C₉Phenyalkylidene ispreferred.

C₅-C₈Cycloalkylene is a saturated hydrocarbon group having two freevalences and at least one ring unit and is typically cyclopentylene,cyclohexylene, cycloheptylene or cyclooctylene. Cyclohexylene ispreferred.

C₇-C₈Bicycloalkylene may be bicycloheptylene or bicyclooctylene.

Unsubstituted or C₁-C₄alkyl-substituted phenylene or naphthylene istypically 1,2-, 1,3-, 1,4-phenylene, 1,2-,1,3-, 1,4-, 1,6-, 1,7-, 2,6-or 2,7-naphthylene, 1,4-phenylene is preferred.

A C₁-C₄alkyl-substituted C₅-C₈cycloalkylidene ring that preferablycontains 1 to 3, most preferably 1 to 2, branched or unbranched alkylgroups, is typically cyclopentylidene, methylcyclopentylidene,dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene,dimethylcyclohexylidene, trimethylcyclohexylidene,tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene.Cyclohexylidene and tert-butylcyclohexylidene are preferred.

A mono-, di- or trivalent metal cation is preferably an alkali metalcation, an alkaline earth metal cation or an aluminium cation, typicallyNa⁺, K⁺, Mg⁺⁺ or Al⁺⁺⁺.

Interesting compounds of formula I are those wherein, when n is 1, R₁ isphenyl which is unsubstituted or substituted in para-position byC₁-C₁₈alkylthio or di(C₁-C₄-alkyl)amino; mono- to penta-substitutedalkylphenyl containing together a maximum number of 18 carbon atoms inthe 1 to 5 alkyl substituents; naphthyl, biphenyl, terphenyl,phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl, pyrrolyl,phenothiazinyl or 5,6,7,8-tetrahydronaphthyl, each unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy oramino.

Preferred compounds of formula I are those wherein, when n is 2,

R₁ is —R₁₂—X—R₁₃—,

R₁₂ and R₁₃ are phenylene,

X is oxygen or —NR₃₁₋, and

R₃₁ is C₁-C₄alkyl.

Further preferred compounds of formula I are those wherein, when n is 1,R₁ is naphthyl, phenanthryl, thienyl, dibenzofuryl, carbazolyl,fluorenyl, each unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₁-C₄alkylthio, hydroxy, halogen, amino, C₁-C₄alkylamino ordi(C₁-C₄-alkyl)amino, or is a radical of formula II

R₇, R₈, R₉ and R₁₀ are each independently of one another hydrogen,chloro, bromo, hydroxy, C₁-C₁₈alkyl, C₂-C₁₈alkyl which is interrupted byoxygen or sulfur; C₁-C₁₈-alkoxy, C₂-C₁₈alkoxy which is interrupted byoxygen or sulfur; C₁-C₁₈alkylthio, C₃-C₁₂-alkenyloxy, C₃-C₁₂alkynyloxy,C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, unsubstituted orC₁-C₄alkyl-substituted phenyl; phenoxy, cyclohexyl, C₅-C₈cycloalkoxy;C₁-C₄alkylamino, di(C₁-C₄alkyl)amino, C₁-C₁₂alkanoyl, C₃-C₁₂alkanoylwhich is interrupted by oxygen or sulfur; C₁-C₁₂alkanoyloxy,C₃-C₁₂alkanoyloxy which is interrupted by oxygen or sulfur;C₁-C₁₂alkanoylamino, C₃-C₁₂alkenoyl, C₃-C₁₂alkenoyloxy,cyclhexylcarbonyl, cyclohexylcarbonyloxy, benzoyl orC₁-C₄alkyl-substituted benzoyl; benzoyloxy or C₁-C₄-alkyl substitutedbenzoyloxy;

or in formula II each pair of substituents R₇ and R₈ and R₁₁, togetherwith the linking carbon atoms, forms a benzene ring,

R₁₁ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkylthio, C₇-C₉phenylalkyl,unsubstituted or C₁-C₄-alkyl-substituted phenyl; cyclohexyl,C₁-C₄alkylamino, di(C₁-C₄-alkyl) amino, C₁-C₁₂-alkanoyl, C₃-C₁₂alkanoylwhich is interrupted by oxygen or sulfur; C₁-C₁₂alkanoylamino,C₃-C₁₂alkenoyl, cyclohexylcarbonyl, benzoyl or C₁-C₄alkyl-substitutedbenzoyl; with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ isnot hydrogen;

R₁₅ is hydroxy, C₁-C₁₂alkoxy or

R₁₈ and R₁₉ are each independently of the other hydrogen or C₁-C₄alkyl,

R₂₀ is hydrogen,

R₂₁ is hydrogen, phenyl, C₁-C₁₈alkyl, C₂-C₁₈alkyl which is interruptedby oxygen or sulfur, C₇-C₉phenylalkyl, C₇-C₁₈phenylalkyl which isinterrupted by oxygen or sulfur and which is unsubstituted orsubstituted by 1 to 3 C₁-C₄alkyl groups, and R₁₉ and R₂₀, together withthe linking carbon atoms, form a cyclohexylene ring which isunsubstituted or substituted by 1 to 3 C₁-C₄alkyl groups,

R₂₂ is hydrogen or C₁-C₄alkyl,

R₂₃ is hydrogen, C₁-C₁₈alkanoyl, C₃-C₁₂alkenoyl, C₃-C₁₂alkanoyl which isinterrupted by oxygen or sulfur;

C₂-C₁₂alkanoyl which is substituted by a di(C₁-C₆-alkyl) phosphonategroup; C₆-C₉cycloalkylcarbonyl, benzoyl,

R₂₄ and R₂₅ are each independently of the other hydrogen or C₁-C₁₂alkyl,

R₂₆ is hydrogen or C₁-C₄alkyl,

R₂₇ is C₁-C₁₂alkylene, C₂-C₈alkenylene, C₂-C₈alkylidene,C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene or phenylene,

R₂₈ is hydroxy, C₁-C₁₂alkoxy or

R₂₉ is hydrogen or —NH—,

R₃₀ is C₁-C₁₈alkyl or phenyl, and

s is 1 or 2.

Also preferred are compounds of formula I, wherein, when n is 1, R₁ isphenanthryl, thienyl, dibenzofuryl, unsubstituted orC₁-C₄alkyl-substituted carbazolyl; or fluorenyl, or R₁ is a radical offormula II

R₇, R₈, R₉ and R₁₀ are each independently of one another hydrogen,chloro, hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,C₃-C₄alkenyloxy, C₃-C₄-alkynyloxy, phenyl, benzoyl, benzoyloxy or

R₁₁ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkylthio, phenyl or cyclohexyl;with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ is nothydrogen,

R₂₀ is hydrogen,

R₂₁ is hydrogen, phenyl or C₁-C₁₈alkyl, or R₂₀ and R₂₂, together withthe linking carbon atoms, form a cyclohexylene ring which isunsubstituted or substituted by 1 to 3 C₁-C₄-alkyl groups,

R₂₂ is hydrogen or C₁-C₄alkyl, and

R₂₃ is hydrogen, C₁-C₁₂alkanoyl or benzoyl.

Compounds of formula I are especially preferred, wherein, when n is 1,R₇, R₈, R₉ and R₁₀ are each independently of one another hydrogen orC₁-C₄alkyl, and R₁₁ is hydrogen, C₁-C₁₂alkyl, C₁-C₄alkylthio or phenyl;with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ is nothydrogen.

Particularly interesting compounds of formula I are those wherein R₂,R₃, R₄ and R₅ are each independently of one another hydrogen, chloro,C₁-C₁₈alkyl, benzyl, phenyl, C₅-C₈-cycloalkyl, C₁-C₁₈alkoxy,C₁-C₁₈alkylthio, C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino,C₃-C₁₈alkenoyloxy or benzoyloxy; with the proviso that, when R₂ ishydrogen or methyl, R₇ or R₉ is not hydroxy or C₁-C₂₅alkanoyloxy, oreach pair of substituents R₂ and R₃ or R₃ and R₄ or R₄ and R₅, togetherwith the linking carbon atoms, forms a benzene ring, R₄ is additionally—(CH₂)_(p)—COR₁₅ or —(CH₂)_(q)OH or, if R₃, R₅ and R₆ are hydrogen, R₄is additionally a radical of formula III,

R₁₅ is hydroxy, C₁-C₁₂alkoxy or

R₁₆ and R₁₇ are methyl groups or, together with the linking carbon atom,form a C₅-C₈-cycloalkylidene ring which is unsubstituted or substitutedby 1 to 3 C₁-C₄alkyl groups,

R₂₄ and R₂₅ are each independently of the other hydrogen or C₁-C₁₂alkyl,

p is 1 or 2, and

q is 2,3,4,5 or 6.

Particularly interesting compounds of formula I are also those whereinat least two of R₂, R₃, R₄ and R₅ are hydrogen.

Compounds of formula I of very particular interest are those wherein R₃and R₅ are hydrogen.

Very particularly preferred compounds of formula I are those wherein

R₂ is C₁-C₄alkyl,

R₃ is hydrogen,

R₄ is C₁-C₄alkyl or, if R₆ is hydrogen, R₄ is additionally a radical offormula III,

R₅ is hydrogen, and

R₁₆ and R₁₇, together with the linking carbon atom, form acyclohexylidene ring.

The compounds of formula I can be prepared in per se known manner.

Conveniently, a phenol of formula V

wherein R₂, R₃, R₄ and R₅ have the given meanings, is reacted with amandelic acid derivative of formula VI which is substituted at thephenyl ring, wherein R₇, R₈, R₉, R₁₀ and R₁₁ have the given meanings, atelevated temperature, preferably in the temperature range from 130 to200° C., in the melt or in a solvent, under normal pressure or a slightvacuum, to the novel compounds of formula I, wherein R₆ is hydrogen.

To prepare the novel compounds of formula I, wherein n is 2, R₆ ishydrogen and R₁ is e.g. —R₁₂—X—R₁₃—, and R₁₂, R₁₃ and X have the givenmeanings, 2 equivalents of the phenol of formula V are used.

It is preferred to carry out the reaction in the presence of a solventsuch as acetic acid, propionic acid or formic acid, in the temperaturerange from 50 to 130° C. The reaction can be catalysed by the additionof an acid such as hydrochloric acid, sulfuric acid or methanesulfonicacid. The reaction may conveniently be carried out as described in thereferences cited at the outset, in particular according to U.S. Pat. No.4,325,863, Example 1, column 8, lines 35-45.

The drawback of this process for the preparation of compounds of formulaI is that it is necessary to use mandelic acids that are substituted atthe phenyl ring or heterocyclic mandelic acids. However, not very manyof these acids are known in the literature and the known syntheses forthe preparation of these mandelic acids are quite troublesome.

A novel process for the preparation of compounds of formula I, which isalso the subject matter of a parallel application, is thereforepreferred.

Typically, a compound of formula VII

 [H]_(n)—R₁   (VIII)

wherein R₂, R₃, R₄ and R₅ have the given meanings, is reacted with acompound of formula VIII, wherein R₁ has the given meaning, to compoundsof formula I.

The reaction conditions of the inventive process are the following:

The reaction can be carried out at elevated temperature, preferably inthe range from 70 to 200° C., in the melt or in a solvent and undernormal pressure or slight vacuum.

It is particularly preferred to carry out the reaction in the boilingrange of the compound of formula VIII.

The preferred solvent is the compound of formula VIII, which issimultaneously the reactant.

Suitable solvents are those which do not participate in the reaction,typically halogenated hydrocarbons, hydrocarbons, ethers or deactivatedaromatic hydrocarbons.

Preferred halogenated hydrocarbons are dichloromethane,1,2-dichloroethane, chloroform or carbon tetrachloride.

Preferred hydrocarbons are typically octane and the commerciallyavailable isomeric fractions such as the hexane faction, white spirit orligroin.

Preferred ethers are typically dibutyl ether, methyl tert-butyl ether ordiethylene glycol dimethyl ether.

Illustrative examples of deactivated aromatic hydrocarbons arenitrobenzene or pyridine.

The water of reaction is preferably removed continuously, preferably byadding an agent that absorbs water, for example a molecular sieve. Mostpreferably the water is removed continuously as an azeotrope bydistillation via a water separator.

This process for the preparation of compounds of formula I is preferablycarried out in the presence of a catalyst.

Suitable catalysts are protonic acids, Lewis acids, aluminium silicates,ion exchange resins, zeolites, naturally occurring sheet silicates ormodified sheet silicates.

Suitable protonic acids are typically acids of inorganic or organicsalts, for example hydrochloric acid, sulfuric acid, phosphoric acid,methanesulfonic acid, p-toluenesulfonic acid or carboxylic acids such asacetic acid. p-Toluenesulfonic acid is particularly preferred.

Illustrative examples of suitable Lewis acids are tin tetrachloride,aluminum chloride, zinc chloride or borotrifluoride etherate. Tintetrachloride and aluminum chloride are especially preferred.

Illustrative examples of suitable aluminium silicates are those that arewidely used in the petrochemical industry and are also known asamorphous aluminium silicates. These compounds contains c. 10-30% ofsilicon monoxide and 70-90% of aluminium oxide. A particularly preferredaluminium silicate is HA-HPV® available from Ketjen (Akzo).

Illustrative examples of suitable ion exchange resins arestyrene-divinylbenzene resins which additionally carry sulfonic acidsgroups, for example Amberlite 200® and Amberlyst® available from Rohmand Haas, or Dowex 50® available from Dow Chemicals; perfluorinated ionexchange resins such as Nafion H® solid by DuPont; or other super-acidion exchange resins such as those as described by T. Yamaguchi, AppliedCatalysis, 61, 1-25 (1990) or M. Hino et al., J. Chem. Soc. Chem.Commun. 1980, 851-852.

Suitable zeolites are typically those widely used in petrochemistry ascracking catalysts and known as crystalline silicon-aluminium oxides ofdifferent crystal structure. Particularly preferred zeolites are theFaujasites available from Union Carbide, for example Zeolith X®, ZeolithY® and ultrastabile Zeolith Y®; Zeohth Beta® and Zeolith ZSM-12®available from Mobile Oil Co.; and Zeolith Mordenit® available fromNorton.

Suitable naturally occurring sheet silicates are termed “acid clays” andtypically include bentonites are montmorillonites, which are degraded,ground, treated with mineral acids and calcined industrially.Particularly suitable naturally occurring sheet silicates are theFulcat® types available from Laporte Adsorbents Co., for example Fulcat22A®, Fulcat 22B®, Fulcat 20®, Fulcat 30® or Fulcat 40®; or the Fulmont®types available from Laporte Adsobents Co., for example Fulmont XMP-3®or Fulmont XMP-4®. A particularly preferred catalyst is Fulcat 22B®. Theother Fulcat® types and Fulmont® types also belong to this preferredclass, because there are only minor differences between the individualtypes, as for example in the number of acid centres.

Modified sheet silicates are also termed “pillared clays” and arederived from the above described naturally occurring sheet silicates byadditionally containing between the silicate layers oxides of e.g.zirconium, iron, zinc, nickel, chromium, cobalt or magnesium. This typeof catalyst is widely used, as described in the literature, inter aliaby J. Clark et al., J. Chem. Soc. Chem. Commun. 1989, 1353-1354, but isavailable from only a very few firms. Particularly preferred modifiedsheet silicates typically include Envirocat EPZ-10®, Envirocat EPZG® orEnvirocat EPIC® available from Contract Chemicals.

Preferred catalysts are naturally occurring sheet silicates or modifiedsheet silicates.

Especially preferred is the process for the preparation of compounds offormula I, wherein the reaction is carried out in the presence of acatalyst of the Fulcat® type.

The catalyst is conventionally added in an amount of 1 to 60% by weightand, if particularly preferred catalyst of the Fulcat® type is used, inan amount of 1 to 30% by weight with respect to the compound of formulaVII.

A particularly interesting process is also that for the preparation ofcompounds of formula I wherein, when n is 1, the molar ratio of thecompound of formula VII to the compound of formula VIII is 1:1 to 1:20,and where n is 2, the molar ratio of the compound of formula VII to thecompound of formula VIII is 3:1 to 2:1.

Before the reaction with a compound of formula VIII, the compounds offormula VII can be subjected to an additional reaction step bysubstituting the hydroxyl group in the compound of formula VII byhalogen or activating said hydroxyl group with a leaving group. Thereaction to give the compounds of formula IX

wherein R₃₂ is halogen or —OR′₃₂, and R′₃₂ is typically C₁-C₂₅alkanoyl,C₃-C₂₅alkenoyl, C₃-C₂₅alkanoyl which is interrupted by oxygen, sulfur or>N—R₁₄; C₆-C₉cycloalkylcarbonyl, thenoyl, furoyl, benzoyl orC₁-C₁₂alkyl-substituted benzoyl; naphthoyl or C₁-C₁₂alkyl-substitutednaphthoyl; C₁-C₂₅alkanesulfonyl, fluoro-substitutedC₁-C₂₅-alkanesulfonyl; phenylsulfonyl or C₁-C₁₂alkyl-substitutedphenylsulfonyl, can be carried out in accordance with known substitutionreactions described, inter alia, in Organikum 1986, pages 186-191; or byesterfication reactions described, inter alia, in Organikum 1986, pages402-408.

Halogen substituents will conveniently be chloro, bromo or iodo. Chlorois preferred.

Alkanoyl of up to 25 carbon atoms inclusive is a branched or unbranchedradical, typically including formyl, acetyl, propionyl, butanoyl,pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl,undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentariecanoyl,hexadecanoyl, heptadecanoyl, octadecanoyl, eicosanoyl or docosanoyl.R′₃₂ defined as alkanoyl preferably contains 2 to 18, most preferably 2to 12, e.g. 2 to 6, carbon atoms. Acetyl is particularly preferred.

Alkenoyl of 3 to 25 carbon atoms is a branched or unbranched radical,typically including propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl,n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-2-ocetonyl, n-2-dodecenoyl,isododecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl. Alkenoyl of3 to 18, preferably 3 to 12, e.g. 3 to 6, most preferably 3 to 4, carbonatoms is preferred.

C₃-C₂₅-Alkanoyl interrupted by oxygen, sulfur or >N—R₁₄ will typicallybe CH₃O—CH₂CO—, CH₃S—S—CH₂CO—, CH₃—NH—CH₂CO—, CH₃—N(CH₃)—CH₂CO—,CH₃—O—CH₂CH₂—O—CH₂CO—, CH₃(—CH₂CH₂—)₂O—CH₂CO—, CH₃—(—CH₂CH₂—)₃O—CH₂CO—or CH₃—(O—CH₂CH₂—)₄O—CH₂CO—.

C₆-C₉Cycloalkylcarbonyl is typically cyclopentylcarbonyl,cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl.Cyclohexylcarbonyl is preferred.

C₁-C₁₂Alkyl-substituted benzoyl which preferably carries 1 to 3, mostpreferably 1 or 2 alkyl groups, is typically o-, m- or p-methylbenzoyl,2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl, 2,5-dimethylbenzoyl,2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethylbenzoyl,2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl,2,4,6-trimethylbenzoyl, 2,6-dimethyl-4-tert-butylbenzoyl or3,5-ditert-butylbenzoyl. Preferred substituents are C₁-C₈alkyl, mostpreferably C₁-C₄alkyl.

C₁-C₁₂alkyl-substituted naphthoyl, which is 1-naphthoyl or 2-naphthoyland preferably contains 1 to 3, most preferably 1 or 2 alkyl groups,will typically be 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-methylnaphthoyl, 1-,2-, 3-, 4-, 5-, 6-, 7- or 8-ethylnaphthoyl, 4-tert-butylnaphthoyl or6-tert-butylnaphthoyl. Particularly preferred substituents areC₁-C₈alkyl, most preferably C₁-C₄alkyl.

C₁-C₁₂Alkanesulfonyl is a branched or unbranched radical, typicallymethanesulfonyl, ethanesulfonyl, propanesulfonyl, butanesulfonyl,pentanesulfonyl, hexanesulfonyl, heptanesulfonyl, octanesulfonyl,nonane-sulfonyl or docosanesulfonyl. Alkanesulfonyl of 1 to 18,preferably 1 to 12, e.g. 2 to 6, carbon atoms is preferred.Methanesulfonyl is particularly preferred.

Fluoro-substituted C₁-C₂₅alkanesulfonyl is typicallytrifluoromethanesulfonyl.

C₁-C₁₂Alkyl-substituted phenylsulfonyl which carries preferably 1 to 3,most preferably 1 or 2, alkyl groups is typically o-, m- orp-methylphenylsulfonyl, p-ethylphenylsulfonyl, p-propylphenylsulfonyl orp-butylphenylsulfonyl. Preferred substituents are C₁-C₈alkyl, mostpreferably C₁-C₄alkyl. p-Methylphenylsulfonyl is particularly preferred.

Thus, for example, the reaction of compounds of formula VII with ahydrohalic acid, a halide of an oxysulfuric acid, a halide of phosphoricacid, a halide of a phosphorous acid, an acid of formula X

R′₃₂—OH   (X)

an acid halide of formula XI,

R′₃₂—Y   (XI)

an ester of formula XII

R′₃₂—O—R₃₃   (XII)

a symmetrical or unsymmetrical anhydride of formula XIII

R′₃₂—O—R′₃₂   (XIII)

or an isocyanate of formula XIV

R₃₄—N═C═O   (XIV)

wherein R′₃₂ in formula XIII may be different or identical.

Y is fluoro, chloro, bromo or iodo,

R₃₃ is C₁-C₈alkyl, and

R₃₄ is C₁-C₂₅alkyl, unsubstituted or C₁-C₄alkyl-substituted phenyl,gives the compounds of formula IX in good yield.

Suitable hydrohalic acids are typically hydrochloric acid, hydrobromicacid or hydriodic acid. Hydrochloric acid is preferred.

Suitable halides of an oxysulfuric acid are typically thionyl chloride,sulfuryl chloride or thionyl bromide. Thionyl chloride is preferred.

Suitable halides of phosphoric acid and phosphorous acid typicallyinclude phosphorous trichloride, phosphorous tribromide, phosphorustriiodide, phosphorus pentachloride, phosphoroxy chloride or phosphoruspentafluoride. Phosphoroxy chloride is particularly preferred.

A preferred meaning of Y is chloro.

Preferred leaving groups are typically carboxylates such as acetates;alkanesulfonates such as mesylates; or arylsuflonates such as tosylates.

In this reaction step it is preferred to use a halide of an oxysulfuricacid such as thionyl chloride; an acid halide of formula XI; an ester offormula XII; or a symmetrical antihydride of formula XIII.

When using a halide of an oxysulfuric acid such as thionyl chloride, itis preferred to carry out the reaction of a compound of formula VIIwithout a solvent and in the temperature range from 0 to 40° C.,preferably at room temperature. The thionyl chloride is convenientlyused in a 2- to 10-fold excess, preferably in a 2- to 6-fold excess,with respect to the compound of formula VII. The reaction can also becarried out in the presence of a catalyst such as dimethyl formamide.

When using an acid of formula X (R′₃₂—OH), the reaction is preferablycarried out with a compound of formula VII in the presence of an inertorganic solvent such as dichloromethane, dioxane, diethyl ether ortetrahydrofuran, and in the presence of a reagent that bonds waterphysically or chemically, conveniently a molecular sieve ordicyclohexylcarbodiimide.

If an acid halide of formula XI (R′₃₂ wherein Y is preferably chloro orbromo, most preferably chloro, is used in process step b), it ispreferred to carry out the reaction of the compound of formula VII inthe presence of a solvent and a base.

The base can be used in varying amounts, from catalytic throughstochiometric amounts to the multiple molar excess with respect to thecompound of formula VII. The hydrogen chloride formed during thereaction may be converted by the base into the chloride, which can beremoved by filtration and/or washing with a suitable aqueous or solidphase, in which case a second water-immiscible solvent can also be used.The product is conveniently purified by recrystallising the residue ofthe organic phase, which is concentrated or evaporated to dryness.

Suitable solvents for carrying out the reaction include hydrocarbons(typically toluene, xylene, hexane, pentane or further petroleum etherfractions), halogenated hydrocarbons (typically di- or trichloromethane,1,2-dichloroethan, 1,1,1-trichloroethane), ethers (e.g. diethyl ether,dibutyl ether or tetrahydrofuran), and also acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone.

Suitable bases include tertiary amines, e.g. trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline,pyridines; hydrides (e.g. lithium, sodium or potassium hydride) oralcoholates (e.g. sodium methylate).

If an ester of formula XII (R′₃₂—O—R₃₃), wherein R₃₃ is C₁-C₄alkyl, mostpreferably methyl or ethyl, is used in process step b), it is preferredto carry out the reaction of the compound of formula VII in the presenceof a solvent that forms an azeotropic mixture with alcohols. The alcohol(R₃₃—OH) that forms during the reaction can be removed continuously bedistillation.

Suitable solvents that form an azeotropic mixture with alcohols do notparticipate in the reaction and typically include hydrocarbons such ascyclohexane, aromatic hydrocarbons such as benzene or toluene;halogenated hydrocarbons such as 1,2-dichloroethane; or ethers such asmethyl tert-butyl ether.

The reaction can be catalysed with a minor amount of a protonic acidsuch as p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid orhydrochloric acid, as well as of a Lewis acid such as borotrifluorideethereate or aluminium chloride.

If a symmetrical anhydride of formula XIII (R′₃₂—O—R′₃₂), wherein R′₃₂is preferably C₂-C₆alkanoyl, preferably acetyl, is used in process stepb), it is preferred to carry out the reaction with a compound of formulaVII without the addition of a further solvent and in the temperaturerange from 20 to 200° C., e.g. the boiling temperature of the anhydrideof formula XIII, preferably from 60 to 180° C.

If an isocyanate of formula XIII, (R₃₄—N═C═O) is used, it is preferredto carry out the reaction with a compound of formula VII without theaddition of a further solvent and in the temperature range from 20 to200° C., e.g. the boiling temperature of the isocyanate of formula XIV,preferably from 60 to 180° C.

The reaction with an isocyanate is likewise preferably carried out inthe presence of a catalyst. Preferred catalysts correspond to thosereferred to above previously in connection with the reaction of thealcohol of formula VII with the compound of formula VIII above.

In the process of this invention for the preparation of the novelcompounds of formula I, wherein R₆ is hydrogen, the compounds of formulaVIII, which also yield mixtures of isomers in other known electrophilicsubstitution reactions, likewise give compounds of formula I in the formof mixtures of isomers. The relative distribution of the isomers willdepend on the commonly known basic rules of organic chemistry forelectrophilic aromatic substitution reactions.

As described in Example 4, reaction of e.g.5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2) with ethyl benzene, using Fulcat 22B as catalyst, gives 59.2% of thepara-isomer (compound (105). Table 1), 10.8% of the meta-isomer(compound (105A) and 21.1% of the ortho-isomer (compound (105B).

The isomers can be purified and separated by fractional crystallisationor chromatography on e.g. silica gel. It is preferred to use themixtures of isomers as stabilisers for organic materials.

The compounds of formula I can be obtained in different crystalmodifications.

The compounds of formula VIII are novel and some are commerciallyavailable or can be prepared by per se known methods.

Some of the compounds of formula VII are known in the literature, andhave been mentioned, inter alia, in Beilstein 18, 17 and Beilstein EIII/IV, 18, 154-166, or described by Th. Kappe et al., Monatshefte fürChemie 99, 990 (1968); J. Morvan et al., Bull. Soc. Chim. Fr. 1979, 583;L. F. Clarke et al., J. Org. Chem. 57, 362 (1992); M. Julia et al.,Bull. Soc. Chim. Fr. 1965, 2175, or by H. Sterk et al., Monatshefte fürChemie 99, 2223 (1968). Novel compounds of formula VII can be preparedby methods analogous to those described in these references.

Preferred, however, is a novel process for the preparation of compoundsof formula VII

which process is the subject matter of a parallel patent application,wherein the general symbols are as defined for formula I, whichcomprises reacting 1 equivalent of the phenol of formula V

wherein the general symbols are as defined in connection with the novelcompounds of formula I, with 0.8 to 2.0 equivalents, preferably 0.8 to1.2 equivalents, of glyoxylic acid.

The glyoxylic acid can be used either in crystalline form or,conveniently, in the form of a commercial aqueous solution, usually a 40to 60% aqueous solution.

The water present in the glyoxylic acid and the water of reaction isremoved by distillation during the reaction, conveniently using asolvent that forms an azeotropic mixture with water.

Suitable solvents that form an azeotropic mixture with water do notparticipate in the reaction and typically include hydrocarbons such ascyclohexane; aromatic hydrocarbons such as benzene or toluene;halogenated hydrocarbons such as 1,2-dichloroethane; or ethers such asmethyl tert-butyl ether.

When carrying out the reaction of the phenol of formula V with glyoxylicacid without a solvent to given the compounds of formula VII in themelt, the water of reaction is conveniently distilled off under normalpressure, preferably under a slight vacuum.

It is preferred to carry out the reaction at elevated temperature,preferably in the range from 60 to 120° C. A particularly preferredtemperature range is from 60 to 90° C.

The reaction can be catalysed by the addition of a minor amount of aprotonic acid such as p-toluenesulfonic acid, methanesulfonic acid,sulfuric acid or hydrochloric acid; or of a Lewis acid such asborotrifluoride etherate or aluminium chloride.

The amount of catalyst is 0.01 to 5 mol %, preferably 0.1 to 1.0 mol %,based on the phenol of formula V.

The compounds of formula VII can be obtained in their tautomeric formsof formula VIIa or formula VIIb

as described by H. Sterk et al., Monatshefte für Chemie 99, 2223 (1968).Within the scope of this application, formula VII will always beunderstood as also embracing the two tautomeric formulae VIIa and VIIb.

Bisphenols of formula XIV

can be prepared in accordance with Houben-Weyl, Methoden der organischenChemie, Vol. 6/1c, 1030.

The compounds of formula I, wherein R₆ is hydrogen, can also be preparedby a so-called one-pot process starting from the phenols of formula V,which comprises reacting one equivalent of the phenol of formula VIIwith 0.8 to 2.0 equivalents of glyoxylic acid to a compound of formulaVII, and subsequently reacting said compound of formula VII, withoutisolation, with a compound of formula VIII.

The definitions of the general symbols in connection with the inventiveone-pot process are the same as for the inventive processes discussedpreviously.

The preferred reaction parameters for the one-pot process correspond tothose previously discussed in detail in connection with the two singlesteps.

Prior to the further reaction with a compound of formula VIII, the3-hydroxy-3H-benzofuran-2-ones of formula VII initially formed in theone-pot process can be subjected to an additional reaction step bysubstituting the hydroxyl group with halogen or activating it with aleaving group.

A special one-pot process for the preparation of compounds of formula Icomprises using a compound of formula V that differs from the compoundof formula VIII.

The dimensions of the compounds of formula XVI for the preparation ofcompounds of formula I, wherein R₆ is a radical of formula IV [compoundsof formula XVII] is carried out by oxidation with e.g. iodine underbasic conditions in an organic solvent at room temperature. Aparticularly suitable base is sodium ethylate, and a particularlysuitable solvent is ethanol or diethyl ether.

The compounds of formula I are suitable for stabilising organicmaterials against thermal, oxidative or light-induced degradation.

Illustrative examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentane or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDEPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholate, esters, ethers, amines, alkyls, alkenylsand/or aryls that maybe either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polylsobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octane copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbonene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymer and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoridepolyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers or cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer, polyacetals modified withthermopolastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,416, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers, or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVCIMBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

Further objects of the invention are therefore also compositionscomprising an organic material that is susceptible to oxidative, thermalor light-induced degradation, and at least one compound of formula I.

Preferred organic materials are natural, semi-synthetic or, preferably,synthetic polymers.

Particularly preferred organic materials are synthetic polymers, mostpreferably thermoplastic polymers. Especially preferred organicmaterials are polyacetals or polyolefins such as polypropylene orpolyethylene.

To be singled out for special mention is the efficacy of the novelcompounds against thermal and oxidative degradation, especially underthe action of heat which occurs during the processing of thermoplasts.The compounds of this invention are therefore admirably suited for useas processing stabilisers.

The compounds of formula I will preferably be added to the organicmaterial to be stabilised in concentrations of 0.0005 to 5%, preferably0.001 to 2%, typically 0.01 to 2%, based on the weight of said material.

In addition to comprising the compounds of formula I, the inventivecompositions may comprise further co-stabilisers, typically thefollowing:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2 Alkylthiomethilphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxphenyl) adipate.

1.4. Tocopherols, for example a-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4hydroxy-3,5-dimethylbenzylmercaptoacetate,tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)malonatedi-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis-[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4′-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-trazine,1,3,5-tris(3,5di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauramilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl) oxamide,3thiaundecanol, 3-thiapentadecano, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14 Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,6-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl) oxamide,3-thiaundecanol, 3-thiapentadecano, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxyabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxphenyl) propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl) oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol,L-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,5,7-trioxabicyclo[2.2.2] octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acide.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoies, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, mixtureof2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃]₂—, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes or ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-piperidyl)succinate,bis(1,2,2,6,6-pentamethylpiperidyl)sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate of N,N-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazasprio[4.5]decan-2,4-dion,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N′-bis-(2,2,6,6 -tetramethyl-4-piperidyl) hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl) oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phospnite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethylphosphite.

5. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

6. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

8. Nucleating agents, for example, 4-tert-butylbenzoic acid, adipicacid, diphenylacetic acid.

9. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

10. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, antistatic agentsand blowing agents.

The co-stabilisers are typically used in concentrations of 0.01 to 10%,based on the total weight of the material to be stabilised.

The novel compounds of formula I can be used in particular together withphenolic antioxidants, light stabilisers and/or processing stabilisers.

It is particularly preferred to use the novel compounds of formula Itogether with phenolic antioxidants. The novel compositions thereforepreferably comprise, in addition to compounds of formula I, phenolicantioxidants, preferably those listed in items 1.1 to 1.17 of the abovelist.

Other preferred compositions comprise, in addition to compounds offormula I, a compound of of the organic phosphite or phosphonite type.

The compounds of formula I and other optional additives are incorporatedinto the organic polymeric material by known methods, convenientlybefore or during shaping to moulded articles or alternatively by coatingthe organic polymeric material with a solution or dispersion of thecompounds and subsequently evaporating the solvent. The compounds offormula I can also be added to the materials to be stabilised in theform of a masterbatch which contains these compounds, typically in aconcentration of 2.5 to 25% by weight.

The compound of formula I can also be added before or duringpolymerisation or before crosslinking.

In this connection, particular attention is drawn to the surprisingfeature that the novel compounds of formula I inhibit discolouration,especially so-called “pinking”, in the manufacture of e.g. polyurethanefoams.

The compounds of formula I can be incorporated into the material to bestabilised in pure form or in waxes, oils of polymer encapsulations.

The compounds of formula I can also be sprayed on to the polymer to bestabilised. They are able to dilute other additives (typically theconventional additives listed above) or melts thereof, so that they canalso be sprayed together with these additives on to the polymer to bestabilised. Application by spraying during deactivation of thepolymerisation catalysts is especially advantageous, in which casespraying is conveniently effected with the vapour used for deactivation.

It may be expedient to spray the compounds of formula I, with or withoutother additives, on to spherical polymerised polyolefins.

A preferred embodiment of this invention is therefore the use ofcompounds of formula I for stabilising organic materials againstoxidative, thermal or light-induced degradation.

The stabilised materials may be in any form of presentation, typicallysheets, filaments, ribbons, mouldings, profiles or binders for coatingcompositions, adhesives or putties.

The invention also relates to a process for stabilising an organicmaterial against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein or applying thereto at least onecompound of formula I.

As already emphasised, the novel compounds are used with particularadvantage as stabilisers in polyolefins, preferably as heat stabilisers.Excellent stabilisation is achieved when the compounds are used inconjunction with organic phosphites or phosphonites. The novel compoundshave in this case the advantage that they are effective in exceedinglylow concentration, typically in concentrations from 0.0001 to 0.050% byweight, preferably from 0.0001 to 0.015% by weight, based on thepolyolefin. The organic phosphite or phosphonite is conveniently used ina concentration of 0.01 to 2% by weight, preferably of 0.01 to 1% byweight, based on the polyolefin. It is preferred to use the organicphosphites and phosphonites disclosed in DE-A-4 202 276. Attention isdrawn in particular to the claims, to the Examples and to pages 5, lastparagraph, to 8. Particularly suitable phosphites and phosphonites willalso be found under item 4 of the above list of co-stabilisers.

Some of the novel compounds of formula I, when incorporated inpolyolefins, induce slight yellowing. This yellowing of polyolefins canbe substantially inhibited by a combination of the novel compounds offormula I with phosphites or phosphonites.

Further objects of the invention are compositions comprising afunctional fluid, preferably of the series of the lubricants, hydraulicfluids and metal processing fluids as well as fuels for driving motorsof the Otto 4-stroke, Otto 2-stroke, diesel, Wankel and orbital type,and at least one compound of formula I.

Particularly preferred lubricants are the mineral oils, the syntheticoils or mixtures thereof.

Suitable functional fluids of the series of the lubricants, hydraulicfluids and metal processing fluids are per se known products.

The suitable lubricants and hydraulic fluids are known to the skilledperson and are described in the relevant literature, inter alia inDieter Klamann, “Schmierstotfe und verwandte Produkte” (Lubricants andRelated Products) (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, “DasSchmiermittel-Taschenbuch” (Handbook of Lubricants) (Dr. AlfredHüthig-Verlag, Heidelberg, 1974), and in “Ullmanns Enzyklopädie dertechnischen Chemie” (Ullmann's Encyclopedia of Industrial Chemistry),Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

Illustrative examples are lubricants and hydraulic fluids based onmineral oils or synthetic lubricants or hydraulic fluids, especiallythose that are carboxylic acid derivatives and are used at temperaturesof 200° C. and above.

Synthetic lubricants typically comprise lubricants based on a diester ofa divalent acid with a monohydric alcohol, typically dioctyl sebacate ordinonyl adipate, on a triester or trimethylolpropane with a monovalentacid or with a mixture of acids, conveniently trimethylolpropanetripelargonate, trimethylolpropane tricaprylate or mixtures thereof, ona tetraester of pentaerythritol with a monovalent acid or with a mixtureof such acids, typically pentaerythritol tetracaprylate, or on a complexester of monovalent and divalent acids with polyhydric alcohols, forexample a complex ester of trimethylolpropane with caprylic and sebacicacid or of a mixture thereof.

Especially suitable lubricants are, in addition to mineral oils,typically poly-α-moietins, ester-based lubricants, phosphates, glycols,polyglycols and polyalkylene glycols and mixtures thereof with water.

The compounds of formula I are readily soluble in lubricants and aretherefore especially suitable for use as additives for lubricants. Theirsurprisingly good antioxidative and anticorrosive properties meritspecial mention.

In lubricants for combustion engines, as in combustion engines thatoperate according to the Otto principle, the novel compounds of formulaI are able to exert their surprising properties. Thus the compounds offormula I inhibit in lubricant oils the formation of deposits (sludge)or reduce such deposits in surprising manner.

It is also possible to prepare masterbatches.

The compounds of formula I act as additives in lubricants even in veryminor amounts. They are conveniently added to the lubricants in anamount of 0.01 to 5% by weight, preferably of 0.05 to 3% by weight and,most preferably, of 0.1 to 2% by weight, based in each case on thelubricant.

The lubricants may also contain other additives which are added forfurther enhancement of the basic properties. These further additivescomprise antioxidants, metal deactivators, rust inhibitors, viscosityimprovers, pour-point depressants, dispersants, detergents, otherextreme-pressure and antiwear additives.

A number of such compounds will be found in the above List under item“1. Antioxidants”, especially under 1.1 to 1.17. Illustrative examplesof such further additives are:

Examples of Aminic Antioxidants

N,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenedianine,N,N′-bis-(1,4-dimethypentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethyl-butyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylateddiphenylamine, for example p,p′-di-tert-octyldiphenylamine,4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol,4-dodecanoylaminophenol, 4-octadecanoylaminophenol,bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4-diaminodiphenylmethane,1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino) propane,(o-tolyl)biguanide, bis[4-(1′, 3′-dimethylbutyl) phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated isopropyl/isohexyldiphenylamines, mixture of mono- anddialkylated tert-butyldiphenylamines,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,N-allylphenotbiazine, N,N,N′, N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,2,2,6,6-tetramethylpiperidin-4-one and2,2,6,6-tetramethylpiperidin-4-ol.

Examples of Other Antioxidants

Aliphatic or aromatic phosphites, esters of thiodipropionic acid or ofthiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid,2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11-trithiatridecane and2,2,15,15-tetramethyl-5,12dihydroxy-3,7,10,14-tetrathiahexadecane.

Examples of Metal Deactivators, for Example for Copper, Are

a) Benzotriazoles and derivatives thereof, for example 4- or5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof,4,5,6,7-tetrahydrobenzotriazole and 5,5′-methylenebisbenzotriazole;Mannich bases of benzotriazole or tolutriazole, e.g.1-[bis(2-ethylhexyl) aminomethyl)tolutriazole and 1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and alkoxyalkylbenzotriazoles such as1-(nonyloxymethyl) benzotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl)tolutriazole.

b) 1,2,4-Triazoles and derivatives thereof, for example 3-alkyl(oraryl)-1,2,4-triazoles, and Mannich bases of 1,2,4-triazoles, such as1-[bis(2-ethylhexyl) aminomethyl-1,2,4-triazole;alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole;and acylated 3-amino-1,2,4-triazoles.

c) Imidazole derivatives, for example 4,4′-methylenebis(2-undecyl-5-methylimidazole) and bis[(N-methyl) imidazol-2-yl]carbinoloctyl ether.

d) Sulfur-containing heterocyclic compounds, for example,2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole andderivatives thereof; and3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one.

c) Amino compounds, for example salicylidenepropylenediamine,salicylaminoguanidine and salts thereof.

Examples of Rust Inhibitors Are

a) Organic acids, their esters, metal salts, amine salts and anhydrides,for example alkyl- and alkenylsuccinic acids and their partial esterswith alcohols, diols or hydroxycarboxylic acids, partial amides ofalkyl- and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- andalkoxyetboxycarboxylic acids such as dodecyloxyacetic acid,dodecyloxy(ethoxy)acetic acid and the amine salts thereof, and alsoN-oleoylsarcosine, sorbitan monooleate, lead naphthenate,alkenylsuccinic anhydrides, for example dodecenylsuccinic anhydride,2-(carboxyethyl)-1-dodecyl-3-methylglycerol and the amine salts thereof.

b) Nitrogen-containing compounds, for example:

I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines andamine salts of organic and inorganic acids, for example oil-solublealkylammonium carboxylales, and also1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.

II. Heterocyclic compounds, for example: substituted imidazolines andoxazolines, and 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline.

c) Phosphorus-containing compounds, for example: Amine salts ofphosphoric acid partial esters or phosphonic acid partial esters, andzinc dialkyldithiophosphates.

d) Sulfur-containing compounds, for example: bariumdionylnaphthalenesulfonatcs, calcium petroleum sulfonates,alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic2-sulfocarboxylic acids and salts thereof.

e) Glycerol derivatives, for example: glycerol monooleate,1-(alkylphenoxy)-3-(2-hydroxyethyl) glycerols,1-(alkylphenoxy)-3-(2,3-dihydroxypropyl) glycerols and2-carboxyalkyl-1,3-dialkylglycerols.

Examples of Viscosity Index Improvers Are

Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylatecopolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers,styrene/acrylate copolymers and polyethers.

Examples of Pour-Point Depressants Are

Polymethacrylates and alkylated naphthalene derivatives.

Examples of Dispersants/Surfactants Are

Polybutenylsuccinic amides or -imides, polybutenylphosphonic acidderivatives and basic magnesium, calcium and barium sulfonates andphenolates.

Examples of Antiwear Additives Are

Sulfur- and/or phosphorus- and/or halogen-containing compounds, e.g.sulfurised olefins and vegetable oils, zinc dialkyldithiophosphates,alkylated triphenyl phosphates, tritolyl phosphate, tricresyl phosphate,chlorinated paraffins, alkyl and aryl di- and trisulfides, amine saltsof mono- and dialkyl phosphates, amine salts of mcthylphosphonic acid,diethanolaminomethyltolyltriazole, bis(2-ethylhexyl)aminomethyltolyltriazole, derivatives of2,5-dimercapto-1,3,4-thiadiazole, ethyl-3-[(diisopropoxyphosphinothioyl)thio]propionate, triphenyl thiophosphate (triphenylphosphorothioate),tris(alkylphenyl) phosphorothioate and mixtures thereof (for exampletris (isononylphenyl) phosphorothioate), diphenyl monononylphenylphosphorothioate, isobutylphenyl diphenyl phosphorothioate, thedodecylamine salt of 3-hydroxy-1,3-thiaphosphetane 3-oxide,trithiophosphoric acid 5,5,5-tris [isooctyl 2-acetate], derivatives of2-mercaptobenzothiazole such as1-N,N-bis-(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole,and ethoxycarbonyl-5-octyldithiocarbamate.

The invention is illustrated in more detail by the following Examples,in which parts and percentages are by weight.

EXAMPLE 1

Preparation of5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (Compound(101), Table 1) Starting from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound (201), Table2) with p-xylene, as well as Fulcat 22B at Catalyst

a) Preparation of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-onecompound (201), Table 2).

A mixture of 212.5 g (1.00 mol) of 2,4-di-tert-butylphenol (97%), 163.0g (1.10 mol) of 50% aqueous glyoxylic acid and 0.5 g (2.6 mmol) ofp-toluenesulfonic acid monohydrate in 300 ml of 1,2-dichloroethane isrefluxed under nitrogen for 3.5 hours on a water separator. Afterwardsthe reaction mixture is concentrated on a vacuum rotary evaporator. Theresidue is taken up in 800 ml of hexane and washed three times withwater. The aqueous phases are separated in the separating funnel andfurther extracted with 300 ml of hexane. The organic phases arecombined, dried over magnesium sulfate and concentrated on a vacuumrotary evaporator. The residue yields 262.3 g (˜100%) of analyticallypure 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one in the form of athick yellowish resin (compound (201), Table 2).

In analogy to Example 1a, compounds (202), (203), (204), (205), (209),(210) and (211) are prepared from the corresponding phenols such as2-tert-butyl-4-methylphenol, 4-tertbutyl-2-methylphenol,2,4-dicyclohexylphenol, 2-(hexadec-2-yl)-4-methylphenol,3-[3-tert-butyl-4-hydroxyphenyl]propionic acid,2,4-bis(α,α-dimethylbenzyl)phenol and4-methyl-2-(1,1,3,3-tetramethylbut-1-yl)phenol with glyoxylic acid. Toprepare compound (207), 2 equivalents of glyoxylic acid are usedstarting from 1,1-bis(3-tert-butyl-4-hydroxyphenyl) cyclohexane.

b) Preparation of5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (compound(101), Table 1)

To a solution of 262.3 g (1.00 mol) of5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2, Example 1a) in 500 ml (4.05 mol) of p-xylene are added 40 g of Fulcat22B and the mixture is refluxed for 15 hours on a water separator. TheFulcat 22B catalyst is then removed by filtration and excess p-xylene isremoved by distillation on a vacuum rotaray evaporator. Crystallisationof the residue from 400 ml of methanol yields 280.6 g (80%) of5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one, m.p.93-97° C. (compound (101), Table 1).

EXAMPLE 2

Preparation of5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (Compound(101), Table 1) Starting from3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one (Compound (206), Table2) with p-xylene, as well as Fulcat 22B as Catalyst

a) Preparation of 3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one(compound (206), Table 2).

A mixture of 21.2 g (0.10 mol) of 2,4-di-tert-butylphenol (97%), 16.3 g(0.11 mol) of 50% aqueous glyoxylic acid and 0.05 g (0.26 mmol) ofp-toluenesulfonic acid monohydrate in 30 ml of 1,2-dichloroethane isrefluxed under nitrogen for 3.5 hours on a water separator. Afterwardsthe reaction mixture is concentrated on a vacuum rotary evaporator. Theresidue is taken up in 9.9 ml (0.105 mol) of acetic anhydride and thesolution is refluxed for 90 minutes. The reaction mixture is then cooledto room temperature, diluted with 100 ml of tert-butyl methyl ether andwashed in succession with water and dilute sodium hydrogencarbonatesolution. The aqueous phases are separated and extracted with 50 ml oftert-butyl methyl ether. The organic phases are combined, dried overmagnesium sulfate and concentrated on a vacuum rotary evaporator.Chromatography of the residue on silica gel with the solvent systemdichloromethane/hexane=2:1 yields 28.0 g (92%) of3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (206), Table2) as a thick reddish resin.

b) Preparation of5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (compound(101), Table 1)

To a solution of 15.3 g (50.0 mmol) of3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (206), Table2, Example 2a) in 25 ml (0.20 mol) of p-xylene is added 1.0 g of Fulcat22B and the mixture is refluxed for 17 hours on a water separator. TheFulcat 22B catalyst is then removed by filtration and excess p-xylene isremoved by distillation on a vacuum rotaray evaporator. Crystallisationof the residue from 20 ml of methanol yields 10.5 g (60%) of5,7di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one, m.p. 93-97°C. (compound (101), Table 1).

EXAMPLE 3

Preparation of3-(3,4-dimethylphenyl)-5,7-di-tertbutyl-3H-benzofuran-2-one (Compound(103), Table 1) Starting from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound (201), Table2) with o-xylene, as well as Fulcat 22B as Catalyst

To a solution of 262.3 g (1.00 mol) of5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2, Example 1a) in 500 ml (4.05 mol) of o-xylene are added 40 g of Fulcat22B and the mixture is refluxed for 1.5 hours on a water separator. TheFulcat 22B catalyst is then removed by filtration and excess p-xylene isremoved by distillation on a vacuum rotary evaporator. Crystallisationof the residue from 500 ml of methanol yields 244 g (69%) of3-(3,4-dimethylphenyl)-5,7-di-tert-butyl)-3H -benzofuran-2-one, m.p.130-132° C. (compound (103), Table 1), which additionally contains c.1.3% of the structural isomer[3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one, compound(103A)]. The mother liquor yields a further 42.4 g of product which,according to GC-MS analysis, consists of 12.3% of the compound (103) and87.7% of the isomeric compound (103A).

EXAMPLE 4

Preparation of 5,7-di-tert-butyl-3-(4-ethylphenyl)-3H-benzofuran-2-on(Compound (105), Table 1) Starting from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound (201), Table2, with Ethyl Benzene, as well as Fulcat 22B as Catalyst

To a solution of 262.3 g (1.00 mol) of5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2, Example 1a) in 500 ml (4.08 mol) of ethyl benzene are added 40 g ofFulcat 22B and the mixture is refluxed for 1.5 hours on a waterseparator. The Fulcat 22B catalyst is then removed by filtration andexcess ethyl benzene is removed by distillation on a vacuum rotaryevaporator. GC-MS analysis shows the residue to consist of a mixture of59.2% of the para-isomer (compound (105). Table 1), 10.8% of themeta-isomer (compound (105A) and 21.1% of the ortho-isomer (compound(105B). Crystallisation of the residue from 400 ml of methanol yields163.8 g (47%) of5,7-di-tert-butyl)-3-(4-ethylphenyl)-3H-benzofuran-2-one (compound(105), Table 1) (para-isomer), which additionally contains 5.6% of themeta-isomer 5,7-di-tert-butyl-3-(3-ethylphenyl)-3H-benzofuran-2-one(compound (105A) and 1.3% of the ortho-isomer 5,7-di-tert-butyl-3-(2-ethylphenyl)3H-benzofuran-2-one (compound (105B). Furthercrystallisation from methanol yields the almost pure para-isomer(compound (105), Table 1), m.p. 127-132° C.

In accordance with the general procedure described in this Example,compounds (102), (106), (107), (114), (115), (116), (117), (118) and(119) are prepared from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one(compound (201), Table 2, Example 1a) and the corresponding aromatichydrocarbons, typically including m-xylene, isopropylbenzene (cumene),tert-butylbenzene, biphenyl, thiophene, p-xylene, dibenzofuran,phenanthrene and diphenyl ether. To prepare compound (119), 2equivalents of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one are usedstarting from diphenyl ether.

EXAMPLE 5

Preparation of5,7-di-tert-butyl-3-(2,3,4,5,6-pentamethylphenyl)-3H-benzofuran-2-one(Compound (111), Table 1) starting from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound (201), Table2) with Pentamethylbenzene, as well as Tin Tetrachloride as Catalyst

11.5 g (77.5 mmol) of pentamethylbenzene and 10 ml (85.0 mmol) of tintetrachloride are added to a solution of 19.7 g (75.0 mmol) of5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2. Example 1a) in 50 ml of 1,2-dichloroethane and the reaction mixtureis refluxed for 1 hour. The reaction mixture is diluted with water andextracted three times with toluene. The organic phases are combined,washed with water, dried over sodium sulfate and concentrated on avacuum rotary evaporator. Crystallisation of the residue from ethanolyields 26.3 g (89%) of5,7-di-tert-butyl-3-(2,3,4,5,6-pentamethylphenyl)-3H-benzofuran-2-one,m.p. 185-190° C. (compound (111), Table 1).

In accordance with the general procedure of this Example, compounds(109) and (110) are prepared from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2, Example 1a) and the corresponding aromatic hydrocarbons, for examplen-dodecylbenzene and 1,2,3-trimethylbenzene.

EXAMPLE 6

Preparation of5,7-di-tert-butyl-3-(4-methylthiophenyl)-3H-benzofuran-2-one (Compound(108), Table 1) Starting from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound (201), Table2) with Thioanisole, as well as Aluminium Trichloride as Catalyst

A solution of 26.2 g (0.10 mol) of5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table2, Example 1a) in 25 ml (0.21 mol) of thioanisoie is added dropwise to asolution of 14.7 g (0.11 mol) of aluminium chloride in 15 ml (0.13 mol)of thioanisole at 35-40° C. The reaction mixture is thereafter stirredfor 30 minutes at 30° C. and for 2 hours at 80° C., and then aftercooling, c. 50 ml of water and then concentrated hydrochloric acid andmethylene chloride are added cautiously in sufficient amount to form ahomogeneous two-phase mixture. The organic phase is separated, washedwith water, dried over sodium sulfate and concentrated on a vacuumrotary evaporator. Crystallisation of the residue from ethanol yields6.7 g (18%) of5,7-di-tert-butyl-3-(4-methylthiophenyl)-3H-benzofuran-2-one, m.p.125-131° C. (compound (108), Table 1).

EXAMPLE 7

Preparation of 5,7-di-tert-butyl-3-(4-methylphenyl)-3H-benzofuran-2-one(Compound (104), Table 1) Starting from 2,4di-tert-butylphenol, withoutisolation of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound(201), Table 2), with Glyoxylic Acid and Toluene, as well as Fulcat 22Bas Catalyst

A mixture of 21.2 g (0.10 mol) of 2,4di-tert-butylphenol (97%), 16.3 g(0.11 mol) of 50% aqueous glyoxylic acid, 2.0 g of Fulcat 22B and 50 mlof toluene is refluxed for 8 hours under nitrogen on a water separator.The Fulcat 22B catalyst is then removed by filtration and excess tolueneis distilled off on a vacuum rotary evaporator. Crystallisation of theresidue from 40 ml of ethanol yields 14.2 g (42%) of5,7-di-tert-butyl-3-(4-methylphenyl)-3H-benzofuran-2-one, m.p. 130-133°C. (compound (104), Table 1).

In accordance with the general procedure of this Example, the compound(112) is prepared starting from 2-tert-butyl-4-methylphenol instead offrom 2,4-di-tert-butylphenol.

EXAMPLE 8

Preparation of4,4′-di(5,7-di-tert-butyl-3H-benzofuran-2-on-3-yl)-N-methyldiphenylamine(Compound (113), Table 1) Starting from5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound (201), Table2) with N-methyl-diphenylamine, as well as p-toluenesulfonic Acid asCatalyst

30.2 g (115.0 mmol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one(compound (201), Table 2, Example 1a) are added over 2 hours to aboiling solution of 9.20 g (50.0 mmol) of N-methyl-diphenylamine and0.20 g of p-toluenesulfonic acid monohydrate in 50 ml of ligroin(mixture of alkanes with a boiling range of 140-160° C.). The reactionmixture is then refluxed for 4 hours on a water separator, then cooledand concentrated on a vacuum rotary evaporator. Crystallisation of theresidue from isopropanol/water=9:1 yields 18.9 g (56%) of4,4′-bis(5,7-di-tert-butyl-3H-benzofuran-2-on-3-yl)-N-methyl-diphenylamine,m.p. 135-145° C. (compound (113), Table 1).

EXAMPLE 9

Preparation of7-tert-butyl-5-methyl-3-(9-methyl-9H-carbazol-3-yl)-3H-benzofuran-2-one(Compound (120), Table 1) Starting from7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (Compound (202),Table 2) with N-methylcarbazole and n-octane, as well as Fulcat 22B asCatalyst

A mixture of 2.2 g (10.0 mmol) of7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202),Example 1a, Table 2), 1.8 g (10.0 mmol) of N-methylcarbazole and 0.2 gof Fulcat 22B and 20 ml of n-octane is refluxed for 5 hours undernitrogen. The Fulcat 22B catalyst is subsequently removed by filtrationand excess n-octane is distilled off on a vacuum rotary evaporator.Chromatography of the residue on silica gel with the solvent systemdichloromethan/hexane=1:2 to 1:1 and subsequent crystallisation of thepure fractions from methanol yields 0.70 g (10%) of7-tert-butyl-5-methyl-3-(9-methyl-9H-carbazol-3-yl)-3H-benzofuran-2-one,m.p. 84-90° C. (compound (120), Table 1). The product may additionallycontain minor amounts of other structural isomers in accordance with thesubstitution at the carbazole ring.

EXAMPLE 10

Preparation of 5,7-di-tert-butyl-3(9H-fluoren-3-yl)-3H-benzofuran-2-one(Compound (121), Table 1) Starting from 2,4-di-tert-butylphenol withoutisolation of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (Compound(201), Table 2), with Glyoxylic Acid and Fluorene, as well asp-toluenesulfonic and Fulcat 22B as Catalyst

A mixture of 15.9 g (75 mmol) of 2,4-di-tert-butylphenol (97%), 12.2 g(82 mmol) of 50% aqueous glyoxylic acid, 40 mg (0.20 mmol) ofp-toluenesulfonic acid monohydrate and 25 ml of 1,2-dichloroethane isrefluxed for 3.5 hours under nitrogen on a water separator. The reactionmixture is thereafter concentrated on a vacuum rotary evaporator. Theresidue is dissolved in 30 ml of n-octane and 125 g (75 mmol) offluorene and 3 g of Fulcat 22B are added to the solution. This reactionmixture is refluxed for 3.5 hours under nitrogen on a water separator,the cooled and filtered. The filtrate is concentrated on a vacuum rotaryevaporator. Chromatography of the residue on silica gel with the solventsystem dichloromethane/hexane=2:1 and subsequent crystallisation of thepure fractions from methanol yields 5.28 g (17%) of5,7-di-tert-butyl-3-(9H-fluoren-3-yl)-3H-benzofuran-2-one, m.p. 140-153°C. (compound (121), Table 1). The product may additionally contain minoramounts of other structural isomers in accordance with the substitutionat the fluorene ring.

EXAMPLE 11

Preparation of a c. 5.7:1 Mixture of3-(3,4-dimethylphenyl)5,7-di-tert-butyl-3H-benzofuran-2-one (Compound(103), Table 1) and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one (Compound(103A)) Isomers Starting from 2,4-di-tert-butyl-phenol with GlyoxylicAcid and o-xylene, as well as Fulcat or Fulmont as Catalyst

To a 1500 ml double-walled reactor with water separator are charged206.3 g (1.0 mol) of 2,4-di-tert-butylphenol, 485 g (5.5 mol) ofo-xylene, 0.5 g (2.6 mmol) of p-toluenesulfonic acid monohydrate and 163g (1.1 mol) of 50% aqueous glyoxylic acid. With stirring, the mixture isheated to 85-90° C., and the apparatus is simultaneously evacuated to c.450 mbar. As soon as the temperature in the reactor is 85-90° C., amixture of o-xylene/water begins to distill from the mixture, theo-xylene being refluxed and the water removed from the system. Thevacuum is then raised continuously so that the temperature in thereactor can be kept at 85-90° C. Altogether c. 98-100 ml of water aredistilled over 3 to 4 hours. The vacuum is then released with nitrogenand 40 g of catalyst (Fulcat 30 or 40, Fulmont XMP-3 or XMP-4) are addedto the clear yellow solution. The apparatus is evacuated to a pressureof 700 mbar and the suspension is stirred at a heating bath temperatureof 165° C. The water of reaction begins to distill from the system as anazeotrope from a temperature of c. 128° C. The temperature in theapparatus rises towards the end to a maximum of 140° C. A total amountof c. 20 ml of water distills from the system over 1 to 2 hours. Thevacuum is then released with nitrogen. The reaction mixture is cooled to90-100° C. and filtered. The apparatus and the filter residue are rinsedwith 100 g of o-xylene. The filtrate is transferred to a 1500 mldouble-walled reactor and concentrated under vacuum and 360 g ofo-xylene are recovered. The reddish-yellow residue is cooled to 70° C.and 636 g of methanol are added cautiously from a dropping funnel, whilekeeping the temperature at 60-65° C. The solution is seeded and stirredfor c. 30 minutes at 60-65° C. to effect crystallisation. Thecrystalline slurry is then cooled over 2 hours to −5° C. and stirring iscontinued at this temperature for a further 1 hour. The crystals arecollected by suction filtration and the residue is washed with 400 g ofcold (−5° C.) methanol in 5 portions. The well dry-pressed product isdried in a vacuum drier at 50-60° C., yielding 266 g of a white solid.Analysis by gas chromatography shows this material to consist of c. 85%of 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one(compound (103), Table 1) as well as of c. 15% of the3-(2,3-dimethylphenyl)-5,7di-tert-butyl-3H-benzofuran-2-one isomer(compound (103A)).

EXAMPLE 12

Preparation of3-(N-methylcarbamoyloxy)-5-methyl-7-tert-butyl-3H-benzofuran- 2-one(Compound (212), Table 2)

A mixture of 5.5 g (25.0 mmol) of7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202),Example 1a), 3 ml (50.0 mmol) of methyl isocyanate and 2 drips ofmethanesulfonic acid are refluxed for 3¼ hours. Then a further 3 ml(50.0 mmol) of methyl isocyanate and 2 drops of methanesulfonic acid areadded. The reaction mixture is refluxed for another 16 hours, thencooled, diluted with dichloromethane and washed with water and a 5%aqueous solution of sodium hydrogencarbonate. The organic phases arecombined, dried over magnesium sulfate and concentrated on a vacuumrotary evaporator. Crystallisation of the residue from toluene yields4.45 g (65%) of 3-(N-methylcarbamoyloxy)-5 -methyl-7-tert-butyl-3H-benzofuran-2-one (compound (212), Table 2), m.p. 138-143°C. (compound (212), Table 2).

EXAMPLE 13

Preparation of 7-tert-butyl-3-chloro-5-methyl-3H-benzofuran-2-one(Compound (208), Table 2)

To a suspension of 2.2 g (10.0 mmol) of7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202),Example 1a, Table 2) in 2.4 ml) 55.0 mmol) of thionyl chloride is addedone drop of dimethyl formamide and the mixture is stirred for 2 hours atroom temperature. Excess thionyl chloride is afterwards distilled off ona vacuum rotary evaporator. Chromatography of the residue on silica gelwith the solvent system dichloromethane/hexane=1:1 and crystallisationof the pure fractions from methanol yields 0.30 g (13%) of7-tert-butyl-3-chloro-5-methyl-3H-benzofuran-2-one, m.p. 81-86° C.(compound (208), Table 2).

TABLE 1 m.p. C (%), H (%) Yield No. Compound (° C.) (calcd/found) (%)101

 93-97 82.24 82.10 8.63 8.66 80 102

 92-96 82.24 82.19 86.3 8.78 52^(a)) 103

130-132 82.24 82.36 8.63 8.62 69^(a)) 104

130-133 82.10 82.13 8.39 8.31 42^(a)) 105

127-132 82.24 82.39 8.63 8.65 47^(a)) 106

109-115 82.37 82.24 8.85 8.91 41^(a)) 107

110-115 82.49 82.49 9.05 9.03 68^(a)) 108

125-131 characterised by ¹H-NMR (CDCl₃) δ (H*) = 4.79 ppm 18^(a)) 109

oil characterised by ¹H-NMR (CDCl₃) δ (H*) = 4.84 ppm 66^(a)) 110

118-122 82.37 82.31 8.85 8.84 74^(a)) 111

185-190 82.61 82.41 9.24 9.43 89 112

 69-80 81.60 81.42 7.53 7.57 70^(a)) m.p. C (%), H (%), N (%) Yield No.Compound (° C.) (calcd/found) (%) 113

135-145 80.44 80.20 7.95 8.06 2.08 1.96 56^(a)) 114

168-170 84.38 84.23 7.57 7.66 25^(a)) m.p. C (%), H (%), S (%) Yield No.Compound (° C.) (calcd/found) (%) 115

 86-93 73.13 73.10 7.37 7.38 9.76 9.69 11^(a)) 116

220-228 82.60 82.58 7.84 7.85 40 m.p. C (%), H (%) Yield No. Compound (°C.) (calcd/found) (%) 117

142-154 81.52 80.97 6.84 6.5 33^(a)) 118

186-189 85.27 85.15 7.16 7.20 17^(a)) 119

resin characterised by ¹H-NMR (CDCl₃) δ (H*) = 4.82 ppm 31^(a)) 120

 84-90 81.43 81.37 6.57 6.72 10^(a)) 121

140-153 84.84 84.66 7.37 7.52 17^(a)) ^(a))The product may additionallycontain minor amounts of other structural isomers in accordance with thesubstitution at the fluorene ring in 3-position of the benzofuran-2-one.

TABLE 2 m.p. C (%), H (%) Yield No. Compound (° C.) (calcd/found) (%)201

resin 73.25 73.33 8.45 8.50   100 202

152-160 70.89 70.40 7.32 7.40    82 203

resin characterised by ¹H-NMR (CDCl₃) δ (H*) = 5.33 ppm^(a))chromatographed on silica gel (CH₂Cl₂/ hexane = 4:1)    45^(a)) 204

resin characterised by ¹H-NMR (CDCl₃) δ (H*) = 5.30 ppm −100 205

resin characterised by ¹H-NMR (CDCl₃) δ (H*) = 5.31 ppm    98 206

resin 71.03 71.10 7.95 7.98    92 207

resin characterised by ¹H-NMR (CDCl₃) δ (tert-butyl) = 1.34 ppm ˜100 208

 81-86 characterised by ¹H-NMR (CDCl₃) δ (H*) = 5.34 ppm    13 209

resin characterised by ¹H-NMR (CDCl₃) δ (H*) = 5.29 ppm ˜100 210

resin characterised by ¹H-NMR (CDCl₃) δ (H*) = 5.08 ppm    38 211

100-103 73.88 73.73 8.75 8.75    61 212

138-143 64.97 65.02 6.91 6.89    65 ^(a))The product may additionallycontain minor amounts of other structural isomers in accordance with thesubstitution at the fluorene ring in 3-position of the benzofuran-2-one.

EXAMPLE 14

Stabilisation of Multiplex-extruded Polypropylene

1.3 kg of polypropylene powder (Profax 6501), which has beenprestabilised with 0.025% of Irganox® 1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate (melt index 3.2 g/10min, measured at 230° C./216 kg) are blended with 0.05% of Irganox® 1010(pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 0.05% ofcalcium stearate, 0.03% of DHT 4A® (Kyowa Chemical Industry Co., Ltd.,[Mg_(4.5)Al₂(OH)₁₃CO₃.3,5 H₂O]) and 0.05% of compound of Table 1. Thisblend is then extruded in an extruder having a cylinder diameter of 20mm and a length of 400 mm at 100 rpm, the 3 heating zones being adjustedto the following temperatures: 260, 270, 280° C. The extrudate is cooledby drawing it through a water bath and is then granulated. Thisgranulate is repeatedly extruded. After 3 extrusions, the melt index ismeasured (at 230° C./2.16 kg). A substantial increase in the melt indexdenotes pronounced chain degradation, i.e. poor stabilisation. Theresults are shown in Table 3.

TABLE 3 Compound of Melt index after Table 1 3 extrusions — 17.1  1034.8 104 5.0 105 4.9 106 4.9

EXAMPLE 15

Stabilisation of Polyethylene During Processing

100 parts of polyethylene powder (Lupolen® 5260 Z) are blended with 0.05part of Irganox® 1010 (pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and 0.05 partof a compound of Table 1 and the blend is kneaded in a Brabenderplastograph at 220° C. and 50 rpm. During this time the kneadingresistance is recorded continuously as torque. In the course of thekneading time the polymer begins to crosslink after prolonged constancy,as can be determined by the rapid increase in torque. The time takenuntil a marked increase in torque is shown in Table 4 as a measure ofthe stabilising action. The longer this time is the better thestabilising action.

TABLE 4 Compound of Time until increase Table 1 in torque (min) —  9.5103 27.0 107 26.0

EXAMPLE 16

Stabilisation of Multiple-extruded Polypropylene at High Temperature

1.5 kg of polypropylene powder (Profax 6501), which has beenprestabilised with 0.008% of Irganox® 1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (melt index 3.2 g/10min, measured at 230° C./2.16 kg) are blended with 0.05% of Irganox®1010 (pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 0.10% ofcalcium stearate and 0.015 to 0.100% of stabiliser to stabiliser mixtureaccording to Table 5. This blend is then extruded in an extruder havinga cylinder diameter of 20 mm and a length of 400 mm at 100 rpm, the 3heating zones being adjusted to the following temperatures: 280, 320,340° C. The extrudate is cooled by drawing it through a water bath andis then granulated. This granulate is repeatedly extruded. After 5extrusions, the melt index is measured (at 230° C./2.16 kg). Asubstantial increase in the melt index denotes pronounced chaindegradation, i.e. poor stabilisation. The results are shown in Table 5.

TABLE 5 Stabiliser or mixture Conzentration Melt index after 5extrusions of stabilisers in % by weight 280° C. 320° C. 340° C.® Irgafos 168^(a)) 0.100 9.2 43.7 79.3 ® Irgafos P-EPQ^(b)) 0.050 6.123.4 61.0 Example 11^(c)) 0.015 8.5 19.7 23.6 ® Irgafos 168^(a)) 0.0457.3 24.4 26.7 Example 11^(c)) 0.005 ® Irgafos P-EPQ^(b)) 0.045 5.6 15.723.6 Example 11^(c)) 0.005 ^(a))® Irgafos 168 istris(2,4-di-tert-butylphenyl)phosphite. ^(b))® Irgafos P-EPQ istetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite.^(c))Example 11 of present application describes a mixture of c. 85% of3-(3,4-di-methylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one (compound(103), Table 1) as well as c. 15% of the3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one isomer(compound (103A)).

What is claimed is:
 1. A compound of formula I

wherein R₁ is a radical of formula II

R₂ is C₁-C₁₈alkyl, R₃ and R₅ are each hydrogen, R₄ is a radical offormula III

R₇ and R₁₀ are each C₁-C₄alkyl, R₆, R₈, R₉ and R₁₁ are each hydrogen,and R₁₆ and R₁₇ together with the linking carbon atom, form aC₅-C₈cycloalkylidene ring which is unsubstituted or substituted by 1 to3 C₁-C₄alkyl groups; with the proviso that the compound of formula A

is excluded.
 2. A compound according to claim 1, wherein R₂ isC₁-C₁₈alkyl, and R₁₆ and R₁₇, together with the linking carbon atom,form a C₅-C₈cycloalkylidene ring.
 3. A compound according to claim 1,wherein R₂ is C₁-C₄alkyl, R₁₆ and R₁₇, together with the linking carbonatom, form a cyclohexylidene ring.
 4. A compound according to claim 3,wherein R₂ is tert-butyl and R₇ and R₁₀ are each methyl.
 5. Acomposition comprising a) an organic material which is susceptible tooxidative, thermal or light-induced degradation, and b) at least onecompound of formula I according to claim
 1. 6. A composition accordingto claim 5, wherein component (a) is selected from the group consistingof lubricants, hydraulic fluids, metal processing fluids and natural,semisynthetic or synthetic polymers.
 7. A composition according to claim6, wherein component (a) is a lubricant selected from the groupconsisting of mineral oils, synthetic oils and mixtures thereof.
 8. Acomposition according to claim 6, wherein component (a) is a syntheticpolymer.
 9. A composition according to claim 6, wherein component (a) isa polyolefin.
 10. A composition according to claim 9, wherein component(a) is polyethylene or polypropylene.
 11. A composition according toclaim 5, wherein component (b) is a compound of formula I in which R₁ isa radical of formula II, R₂ is C₁-C₄alkyl, R₃ and R₅ are each hydrogen,R₇ and R₁₀ are each C₁-C₄alkyl, R₆, R₈, R₉ and R₁₁ are each hydrogen,and R₁₆ and R₁₇, together with the linking carbon atom, form acyclohexylidene ring.
 12. A composition according to claim 5, whichcontains component (b) in an amount of 0.0005 to 5% by weight, based onthe weight of component (a).
 13. A composition according to claim 5,which comprises further additives in addition to components (a) and (b).14. A composition according to claim 13, which comprises as furtheradditives phenolic antioxidants, light stabilizers and/or processingstabilizers.
 15. A composition according to claim 14, which comprises asfurther additives at least one organic phosphite or phosphonitecompound.
 16. A process for stabilizing an organic material againstoxidative, thermal or light-induced degradation, which comprisesincorporating therein or applying thereto at least one compound offormula I as defined in claim
 1. 17. A process according to claim 16wherein, in the compound of formula I R₁ is a radical of formula II, R₂is C₁-C₄alkyl, R₃ and R₅ are hydrogen, R₇ and R₁₀ are each C₁-C₄alkyl,R₆, R₈, R₉ and R₁₁ are each hydrogen, and R₁₆ and R₁₇, together with thelinking carbon atom, form a cyclohexylidene ring.